Preparation of alkyl monochlorides



July 13, 1954 H. TRAMM Erm.

PREPARATION OF ALKYL MOOCH-LORIDES Fled March 6, 1951 COOLING WATER v INVENTOR HE/NR/CH 7Bf-1MM N/KOLAUS GE/SER HELMUT KOLL/NG SE'lGFR/ED PUS THERMOMETER HOF w. ATTORNEY Patented July 13, 1954 2,688,888 i eREPARATroN oF ALKYL MoNoonLoamEs Heinrich Tramm, Mulheim-Ruhr-Speldorf, and

Nikolaus Geiser, Helmut Kolling, and Siegfried Puschhof, Duisburg-Hamborn, Germany,

signore to Ruhrchemie Aktiengesellschaft, Oberhausen-Holten, Germany, a German corporation Application March` 6, 1951I Serial No. 216,112

Claims priority, application German March 6, 1950 con en o e Addition ol gram-atourcbllgrine per mol of hydrofeaction prom uct, mol percent As can be seen, in order to obtain a high yield of monochlorides, it is advisable to add by addition less than 0.3 gram-atom of chlorine to each mol of hydrocarbon.

When operating 'in this manner very large quantities of hydrocarbons must be passed through the chlorination. For this reason, the industrial operation of this reaction can be effected advantageously only in continuous operation.

It has been suggested to pass the hydrocarbon mixture and gaseous chlorine in parallel ilow or preferably in counter-dow through vertical pipes of glass or quartz glass. This operation, however. has only a very low output, inasmuch as the liquid velocities used therein amount to only 0.1 ema/sec. when taking into consideration the quantities of gas which are present at the same time.

In other known chlorination methods the liquid products are pumped through a cooler and a reaction vessel in which a mercury vapor lamp is suspended. An aliquot portion of the liquid is continuously tapped off from the circuit and worked up. The capacity of this apparatus is very low, as a.very high re-cycling ratio is generally used. y

Aside from the extremely small output these conventional methods for continuous hydrocarbon chlorination have the further disadvantage in that they cannot reach the ratios of monopolychlorides theoretically possible in a non-continuous chlorination. An undesired displacement of the ratio in the direction of the formation of polychlorides takes place. v

Even when re-cycling the products in such a manner that the chlorine and hydrocarbons are introduced at the bottom end of a vertical glass tube and the reaction products are removed from the top, no substantial improvement in the yield is obtained.

One object of this invention is continuous hydrocarbon chlorination withv an increased capacity and an increased yield of monochlorides. This and further objects will become apparent from the following description and the examples.

The accompanying gure illustrates an em- ;Jodiment of an apparatus for eecting the reacion.

It has now been found that it is possible to practically obtain vthe theoretically possible yield of monochlorides and at the same time increase the capacity of the chlorination apparatus in a continuously carried out hydrocarbon chlorination, if the hydrocarbon which is to be chlorinated and the chlorine gas are passed in parallel ow downwards through an illuminated packed reaction tube with a, liquid velocity in excess of 5 cms/sec. and preferably in excess of 10 cms/sec., not taking into consideration the quantities of gas also owing through. The reaction tube may be vertical, inclined or horizontal. .The reaction tube must be made of glass or some other material which is transparent to light. In order to remove the heat of reaction it is advantageous to provide the reaction tube with a cooling jacket. The tube should be arranged in such a manner that it can be readily and intensely illuminated, as for example, with mercury vapor lamps.

An embodiment of an apparatus for effecting the chlorination in accordance with the invention is diagrammatically shown in the drawing. The apparatus consists of a vertical glass tube provided with a glass cooling jacket. The interior of the vertical glass tube is iilled with packing material such as 'lller consisting of glass or ceramic material. The filler material is retained on a screen positioned at the bottom of the vertical glass tube just above the outlet opening. The tube is provided with a thermometer which extends up the central axis thereof. A bank of lamps is positioned adjacent the outside of the cooling jacket for illuminating tube leaving a darkened zone at the upper portion. The chlorine and liquid hydrocarbon are passed into the upper portion of the vertical tube through the inlets indicated and the chlorinated product and hydrogen chloride are removed from the lower end of the vertical tube through the outlet as shown. Cooling water is circulated through the cooling jacket to maintain the temperature in the prescribed limits.

When proceeding according to the invention. the chlorine addition is preferably restricted to 0.1 to 0.3- gram-atomsl of chlorine for each mol of hydrocarbon. The chlorine hydrocarbons formed are separated from the unreacted hydrocarbon after leaving the reaction tube by fractionation. The -unreacted hydrocarbon is returned to be re-cycled. Care must be taken that the chlorine and the hydrocarbon are sumciently throttled, so that the reaction can not back up. This can preferably be' accomplished by having a sufilciently high preliminary pressure for both the reaction participants with suitable throttle valves arranged in the admission lines. In this way the reaction can be carried out in an absolutely uniform manner without exercising extremely careful operational supervision.

If the chlorination is carried out in vertical or slanted reaction tubes a. liquid seal must be provided at the lower end of the tube in order to prevent the entire liquid from running out. Flirthermore, the packing must be supported by a screen or grate positioned at the lower end of the tube, so that it will not be removed by the high ow velocity.

As the addition of chlorine to hydrocarbons is an exothermal reaction, care must be taken for the most rapid removal of the heat of reaction. This can be accomplished by providing large cooling surfaces and having a. suilicient temperature difference between the cooling agent and the reaction tube. If possible. the reaction temperature should not exceed 70 C. inasmuch as the formation of polychlorides increases at higher temperatures. It has proven particularly advantageous to effect the reaction at 45 to 65 C.

Because of the parallel flow between the hydrocarbon and the chlorine gas, the actual velocities in the reaction tube are substantially greater than the pure liquid velocity inasmuch as the hydrochloride which is produced becomesmixed with the liquid chlorination products. Due to this the gaseous liquid reaction mixture has an actual velocity of about 2 to 6 m./sec. In the conventional procedure in vertical reaction tubes in which the chlorine was admitted from the bottom, the hydrocarbon formed was able to escape from the top and had no substantial influence on the velocity of the reaction products. When operating according to the invention, however, the liquid and gaseous reaction products are passed, mixed together, through the reaction tubes with a high velocity. The length of the reaction zone accordingly is considerably greater which in turn makes the removal of the reaction heat produced considerably simpler. In spite f this the end result of the chlorination is not impaired inasmuch as the high velocities avoid an increased formation of higher chlorinated hydrocarbons. The reaction zone can be further extended by starting with low light intensities at the beginning of the reaction now and increasing the intensity along the path of ow. The light sources should be arranged at a slight distance from the reaction tube.

The hydrocarbon to be worked must -be completely free from oxygen prior to the-reaction. This is accomplished by thoroughly blowing nitrogen or other inert gases through the hydro- 4 carbon. Even small quantities of oxygen have a very strong inhibiting action on thel chlorine addition.' 'The removal of traces of oxygen may also be effected by previously passing hydrogen chloride, produced during the reaction, through the hydrocarbon. v

Hydrocarbon' mixtures containing relatively large quantities of unsaturates and alcohols, for example, the products of catalytic carbon monoxide hydrogenation, must be freed from their alcohol and oletlne content prior to chlorination, inasmuch as undesired dichiorides are produced from these oleflnes and alcohols during the chlorination. It is possible to effect the prior removal of the alcohols and olenes by dehydration over aluminum oxide followed by hydrogenation with nickel or cobalt catalysts. This procedure, however, requires relatively high pressures and temperatures and causes a high consumption of hydrogen. Olene-like and/or alcohol-like hydrocarbons can be freed of these undesired compoundsmost simply by separating4 them into fractions containing the same number of carbon atoms and thereafter treating them with zinc chloride and hydrogen chloride in liquid phase, distilling off the alkyl monochlorides produced thereby, ehlorinating the remaining saturated hydrocarbons, and returning the hydrogen chloride which escapes for re-cycling to the process. In this manner the initial mixtures which are to be chlorinated can be freed of the disturbing unsaturated and alcoholic portions in an extremely simple and easy manner. The hydrochloric acid produced in the chlorination of the saturated hydrocarbons may be used in connection with the conversion of the oleiines and alcohols into chlorides in accordance with the invention. In operating in this manner chlorine is saved and these alcohols and oleiines can be converted exclusively into alkyl monochlorides.

For removing the heat of reaction it has been found particularly advantageous to use two glass tubes, one of a smaller diameter, yconcentrically arranged one within the larger. The hydrocarbon chlorination is eected in the space between the two tubes which is illled with fillers of suitable size. Water or other suitable cooling agents are flowed through the smaller tube. 'Ihe filler may consist of ceramic material and preferably of glass. It is advantageous to effect the illumination of the reaction tube from the outside so as to avoid additional heating of the reaction mixture by the illuminating body. With sufllcient cooling, of course, inner illumination can also be used.

The following examples are given by way of illustration and not limitation, the invention being limited by the appended claims or their equivalents.

Example 1 water flowed. The annular space between the 1 outer and inner tubes was filled with glass rings of a diameter of 3 mm. The entire apparatus was inclined to the horizontal by an angle of about 5.

As hydrocarbon, there was selected a Cio fraction obtained by fractionation of a primary product of carbon monoxide hydrogenation. This Cm traction still contained small amounts oflCz alcohols. It was stirred in an agitator vessel with about of its weight of an aqueous '7,0% zinc chloride solution at 70 to 80 C., gaseous hydrogen chloride being simultaneously introduced. AAfter the separation of the aqueous catalyst solution and the washing out of the residual hydrochloric acid and zinc chloride, the reaction product was subjected to vacuum distillation, in which, first of all, the C1 monochloride produced from the C1 alcohol, then the saturated Cio hydrocarbon, and ilnally, the Cm monochloride produced from the unsaturated C10 hydrocarbon were recovered. The saturated Cio hydrocarbon was now subjected to chlorination, the hydrogen chloride obtained therefrom serving for the addition reaction with the olefines.

Prior to the chlorination, the Cio hydrocarbon was blown-through with nitrogen in a pressure vessel. It was then introduced via a throttle valve into the darkened upper end of the reaction tube. A stream of chlorine was then introduced through a nozzle shortly behind the place of admission oi the hydrocarbon, said chlorine being obtained from a gas cylinder via a throttle valve.

80 liters of Cin hydrocarbon and 5.8 kgs. oi' chlorine per hour were introduced into the reaction tube. The outer tube was irradiated by 5 lamps which had a power of 500 watts. Not taking the gaseous phase into consideration, a liquid velocity of 16 cm./sec. was maintained. The highest temperature of the reaction mixture was 65 C. The discharging reaction products had a temperature of approximately 45 C. The discharging gas was practically free of chlorine.

The discharging liquid mixture. consisting of unreacted hydrocarbon and alkyl chlorides, was first of al1 blown-through with air in order to remove dissolved hydrocarbon. Thereupon, it was subjected to distillation at an absolute pressure of 10 mm. mercury. From this distillation there were obtained 48 kgs. unreacted C10 hydrocarbon, 11.4 kgs. Cio monochloride and 1.7 kgs. Cm polychlorides per hour. Referred to the total quantity of hydrocarbon chlorides, this corresponds to a yield of 89 mol-percent monochloride as compared with a theoretically possible yield of 90.5 mol-percent monochloride.

Eiltample 2 The chlorinating apparatus consisted oi' a transparent quartz-glass tube of a length of 4 meters and an inner diameter of 50 mm. Concentrically within it, there was provided a glass tube having an outer diameter of 35 mm. The space between the outer and inner tubes was filled with glass rings of a diameter of 6 mm. The vertical reaction tube was surrounded by a glass tube of a diameter of 100 mm., which consisted of several sections joined together by rubber sleeves and served, as did the inner tube, for the cooling of the reaction tube. Tube lamps (strip, scailold or tubular lamps) were arranged in three sides for illumination. The hydrocarbon to be chlorinated was obtained by fractionation of a petroleum heavy-gasoline which had been previously freed of its content of aromatics and had a content of aliphatics of 60% and of naphthenes of 40%, It was introduced via a throttle valve, by means of a pump, into the upper darkened end of the reaction tube. The chlorine admission nozzle was located a short distance behind. it. 500 liters of Cio hydrocarbon and 36.5

kgs. chlorine were introduced per hour. The hydrocarbon had been previously freed of its oxygen content by blowing hydrogen chloride through it.

Disregarding the gases producedv during the reaction, the liquid velocity was, l2 cm./sec. The reaction gas discharging with the reaction products was practically free of chlorine. The liquid reaction products were freed of the hydrogen chloride still present by blowing air through them. Thereupon, they ,were fractionated at an absolute pressure of 10 mm. mercury. From this fractionation, there were obtained 300.5 kgs. unreacted Cio hydrocarbons, 71.0 kgs. Cio monochloride and 11.3 kgs. Cio polychlorides per hour. Referred to the total quantity of alkyl chlorides produced, there were obtained 88.4 mol-percent monochlorides as compared with the theoretically possible quantity of 90.5 mol-percent monochlorides.

The examples show that the method in accordance with the invention gives practically the theoretical mol-ratio'of monochlorides to polychlorides. With an addition of 0.1 gram-atom chlorine to each mol of hydrocarbon, one can therefore obtain more than mol-per cent monochlorides. In spite of this, the quantities treated are substantially higher, due to the high liquid velocities used, than in connection with the previously known chlorination processes. A single reaction tube of a length of 4 meters and a free cross-section of only approximately 12 square centimeters makes possible an' hourly output of 500 liters. Extremely small quantities of chlorine can be added to each hydrocarbon molecule by the method of the invention, as required for a high yield of alkyl monochlorides, without using excessively large chlorinating apparatus.

When the liquid velocity is used herein, there is meant the liquid velocity disregarding the quantity ot gas flowing.

We claim:

1. Method for the production of alkyl monochlorides which comprises establishing a downward path of now containing ller material, substantially continuously passing a saturated liquid hydrocarbon to be chlorinated and chlorine gas in parallel ilow downward through said path of ilow in amounts of 0.1 to 0.3 gram-atoms of chlorine for each mol of hydrocarbon at a liquid flow velocity in excess of about 5 cms. per second exclusive of the quantities of gas owing through, maintaining a temperature along said path of ow below 70 C. and a. pressure suiiicient to maintain said hydrocarbon in liquid phase, continuously illuminating the reactants along said path of flow, and continuously recovering a high yield of alkyl monochlorides.

2. Method according to claim 1, in which the reactants are passed down said path of ow at a liquid velocity in excess of about 10 cms/sec. exclusive of the quantities of gas owing through.

3. Method according to claim 1, in which the intensity of said illumination is increased along said path of flow in the flow direction.

4. Method according to claim 1, in which a substantially oxygen free gas is blown through the hydrocarbon prior to passing it down said path of flow to remove the oxygen therefrom.

5. Method according to claim 4, in which said oxygen free gas is at least one member of the group consisting of nitrogen and hydrogen chloride.

6. Method according to claim 1, in which said liquid hydrocarbon is substantially a C10 fraction.

. 7 8 1. Method wool-ding to claim 1, in which said Number Name Dato is normal pressure and in which said 3,105,733 Hass-et al. Jan. 18, 1938 hydrocarbon is a. normally liquid hydrocarbon. 2,473,162 McBee et al June 14. 1949 2,530,699 Humphrey et al Nov. 21, 1950 References Glied in the 111e of this patent 5 UNITED STATES PATENTS OTHERREFERENCES Number Name Date t I 1 27D 0 1,432,761 noch oct.24, 1922 ry v N 1 W 119 95 1.954.438 Britton et as. ---1---- Apr. 1o, 1934 lo Hass et al., Indusfrhl and Engineering Chem- 

1. METHOD FOR THE PRODUCTION OF ALKYL MONOCHLORIDES WHICH COMPRISES ESTABLISHING A DOWNWARD PATH OF FLOW CONTAINING FILLER MATERIAL, SUBSTANTIALLY CONTINUOUSLY PASSING A SATURATED LIQUID HYDROCARBON TO BE CHLORINATED AND CHLORINE GAS IN PARALLEL FLOW DOWNWARD THROUGH SAID PATH OF FLOW IN AMOUNTS OF 0.1 TO 0.3 GRAM-ATOMS OF CHLORINE FOR EACH MOL OF HYDROCARBON AT A LIQUID FLOW VELOCITY IN EXCESS OF ABOUT 5 CMS. PER SECOND EXCLUSIVE OF THE QUANTITIES OF GAS FLOWING THROUGH, MAINTAINING A TEMPERATURE ALONG SAID PATH OF FLOW BELOW 70* C. AND A PRESSURE SUFFICIENT TO MAINTAIN SAID HYDROCARBON IN LIQUID PHASE, CONTINUOUSLY ILLUMINATING THE REACTANTS ALONG SAID PATH OF FLOW, AND CONTINUOUSLY RECOVERING A HIGH YIELD OF ALKYL MONOCHLORIDES. 